Catalyst comprising a molecular sieve belonging to the abc-6 framework family with disorder in the abc stacking sequence and use of the catalyst

ABSTRACT

Catalyst and use of the catalyst comprising a molecular sieve belonging to the ABC-6 framework family with disorder in the ABC stacking sequence essentially composed of double-six-ring periodic building units and having a mole ratio of silicon oxide to aluminum oxide from about 8 to about 60.

The present invention relates to a catalyst comprising a molecular sievebelonging to the ABC-6 framework family with disorder in the ABCstacking sequence.

In particular, the invention is a catalyst comprising a crystallinemolecular sieve material belonging to the ABC-6 framework family withdisorder in the ABC stacking sequence essentially composed ofdouble-six-ring periodic building units with a high silica-to-aluminaratio and the use of the catalyst in chemical reactions.

Zeolites are crystalline microporous materials formed by corner-sharingTO₄ tetrahedra (T=Si, Al, P, Ge, B, Ti, Sn, etc.), interconnected byoxygen atoms to form pores and cavities of uniform size and shapeprecisely defined by their crystal structure. Zeolites are also denoted“molecular sieves” because the pores and cavities are of similar size assmall molecules. This class of materials has important commercialapplications as absorbants, ion-exchangers and catalysts.

Molecular sieves are classified by the International Zeolite Association(IZA) according to the rules of the IUPAC Commission on Molecular SieveNomenclature. Once the topology of a new framework is established, athree letter code is assigned. This code defines the atomic structure ofthe framework, from which a distinct X-ray diffraction pattern can bedescribed.

There are a large number of molecular sieve structures known today. Someknown molecular sieves belong to certain families of structures withsimilar features. One specific family, the ABC-6 family, can bedescribed as a stacking of two-dimensional periodic layers ofnon-connected planar 6-ring motifs, made up from 6 T-atoms (T=Si, Aletc.) connected by oxygen atoms. The resulting layer with hexagonalsymmetry is also called the periodic building unit (PerBU).

The stacking is typically described by a sequence of letters “A”, “B”and “C” that indicates the relative positions of neighboring layers.“A”, “B” and “C” refers to the well-known relative positions ofneighboring layers when stacking hexagonal layers of close packedspheres. Once the repeating stacking sequence is known, the3-dimensional framework topology is defined. Well-known examples offramework topologies that belong to the ABC-6 family are CAN (stackingsequence AB . . . ), SOD (stacking sequence ABC . . . ). In theseexamples the structure is constructed only of single 6-rings. Once thereis a repetition of A, B or C in the stacking sequence, double-6-ringsappear. Well known framework topologies with double-6-rings in thestructure are GME (stacking sequence: AABB . . . ) and CHA (stackingsequence AABBCC . . . ). In a similar manner a framework topology canalso consist of both single-6-rings and double-6-rings. Well-knownexamples include OFF (stacking sequence: AAB . . . ) and ERI (stackingsequence: AABAAC . . . ).

With respect to the present invention it is useful to discuss as anexample the specific framework topologies CHA and GME. The CHA and GMEframework topologies are both well-defined ordered structures. The CHAframework topology is a small-pore material characterized by athree-dimensional 8-membered-ring pore systems containingdouble-six-rings (d6R) and cha cages. The GME framework topology is alarge-pore material characterized by 12-membered-ring channels in onedimension and 8-membered ring pore systems in the other two dimensionscontaining double-six-rings (d6R) and gme cages.

Any finite sequence of A, B and C layers, stacked periodically, forms anordered structure with well-defined unit cells in all three spatialdimensions. Any non-periodic mistake in the stacking sequence will leadto a disordered structure without a well-defined periodic unit cell inthe direction normal to the layers. When sufficient stacking disorderoccurs the material can no longer be considered to have the sameframework topology as the ordered framework. As a consequence ofdisorder in the ABC-6 sequence, different local topological featuresarise such as a distribution of different cage-sizes that are completelydifferent to the ordered parent framework topology. This will lead todifferent adsorption, diffusion and material properties, in particularcatalytic properties.

As an example, CHA and GME topologies both consist of a sequence ofdouble 6-ring layers. Each layer is shifted ⅓ of the periodicityrelative to the previous layer. In case of CHA the ⅓ shift consistentlyhappens in the same direction, which means that after three steps thelayer has shifted a full periodicity relative to the first layer. Incase of GME the ⅓ shift consistently happens in alternating directions,which means that after two steps the layer is back to the originalposition. The simplest way of describing the amount of disorder in theCHA-GME series is to define the choice of changing stacking direction(faulting) to a simple probability. This means a faulting probability of0% results in pure ordered CHA, while a probability of 100% results inpure ordered GME. In the following description, this specific percentageis used to describe the amount of disorder in the molecular sieve. Inreality, the probability of changing stacking direction will be slightlydependent on stacking directions of previous steps, because ofrelaxation effects. For this reason, the above explanation using afaulting probability in its simplest form should not be used to limitthe invention disclosed herein.

X-ray diffraction patterns of the stacking disordered CHA-GME series canbe simulated using DIFFaX [M. M. J. Treacy, J. M. Newsam & M. W. Deem1991 “A General Recursion Method for Calculating Diffracted Intensitiesfrom Crystals Containing Planar Faults” Proc. Roy. Soc. Lond. A433,499-520], available from[http://www.public.asu.edu/˜mtreacy/DIFFaX.html]. The simulated patternscan be used for comparison with experimentally measured X-raydiffraction data to elucidate the approximate amount of disorder inprepared materials.

X-ray diffraction patterns with increments of 10% stacking disorder areshown in FIG. 1. As mentioned above, a faulting probability of 0%corresponds to pure CHA while a faulting probability of 100% correspondsto pure GME There are a number of reported examples in the literaturefor the preparation and use of materials described as disordered ABC6-ring molecular sieves with disorder in the 6-ring stacking sequence.Disordered materials only containing double-6-rings are typicallydescribed as part of the disordered CHA-GME series.

So far, the known molecular sieves that have been synthesized andidentified as members of the disordered CHA-GME series are: Babelite [R.Szostak and K. P. Lillerrud, J. Chem. Soc. Chem. Commun. 1994(20), 2357(1994)]; Linde D [K. P. Lillerud, R. Szostak and A. Long, J. Chem. Soc.Faraday Trans. 90, 1547 (1994); GB Patent 868,646]; Phi [K. P. Lillerud,R. Szostak and A. Long, J. Chem. Soc. Faraday Trans. 90, 1547 (1994);U.S. Pat. No. 4,124,686]; ZK-14 [G. H. Kuehl. In: Molecular Sieves.S.C.I., London, 1967, p 85]; LZ-276 [G. W. Skeels, M. Sears, C. A.Bateman, N. K. McGuire, E. M. Flanigen, M. Kumar, R. M. Kirchner,Micropor. Mesopor. Mater. 30, 335 (1999); U.S. Pat. No. 5,248,491];LZ-277 [G. W. Skeels, M. Sears, C. A. Bateman, N. K. McGuire, E. M.Flanigen, M. Kumar and R. M. Kirchner, Micropor. Mesopor. Mater. 30, 335(1999); U.S. Pat. No. 5,192,522].

In the case of Babelite, the material is said to crystallize withsimilar SiO2/Al2O3 ratios as the synthetic Chabazite that are typicallyclose to 4.0 [Verified Syntheses of Zeolitic Materials, 2nd RevisedEdition, Harry Robson, editor, Karl Petter Lillerud, XRD Patterns (2001)ISBN: 0-444-50703-5]. The highest reported SiO2/Al2O3 ratio of Linde Dis 4.9. U.S. Pat. No. 4,124,686 discloses zeolite Phi to have aSiO2/Al2O3 ratio of 4.6. As to LZ-277, U.S. Pat. No. 5,192,522 disclosesa maximum SiO2/Al2O3 ratio of 6.6. Of all the known materials LZ-276 hasbeen reported with the highest SiO2/Al2O3 ratios where U.S. Pat. No.5,248,491 discloses a SiO2/Al2O3 ratio of 7.7 and Skeels et al. report aSiO2/Al2O3 ratio of 7.8 when exploring the synthesis of LZ-276. In thepreparation of LZ-276 tetraethylorthosilicate is used as the sole sourceof silicon, and sodiumaluminate is used as the sole source of Al. Theresulting morphology of LZ-276 is later reported to be sphericalintergrowths of disc-shaped particles [G. W. Skeels, M. Sears, C. A.Bateman, N. K. McGuire, E. M. Flanigen, M. Kumar, R. M. Kirchner,Micropor. Mesopor. Mater. 30, 335 (1999)].

It is commonly acknowledged in the art that the hydrothermal stabilityof aluminosilicate molecular sieves become higher when the SiO2/Al2O3ratio is increased. Consequently, there is a need to increase theSiO2/Al2O3 ratios of the known molecular sieve materials, in particularfor applications where hydrothermal stability is an issue.

Furthermore, the specific amount of disorder in zeolites belonging tothe ABC-6 family dictates specific topological features, such asdistribution of cages with various dimensions, and ultimately catalyticand diffusion properties of such molecular sieves.

To the best of our knowledge, there are no reports on the possibility tocontrol the amount of disorder when preparing disordered molecular sievematerials.

Accordingly, there is a strong desire to provide a catalyst comprisingdisordered ABC 6-ring molecular sieves with a high mole ratio of siliconoxide to aluminum oxide.

Thus, the invention is in first aspect a catalyst comprising a molecularsieve belonging to the ABC-6 framework family with disorder in the ABCstacking sequence essentially composed of double-six-ring periodicbuilding units and having a mole ratio of silicon oxide to aluminumoxide from about 8 to about 60.

Specific features and embodiment of the invention either used alone orin combination thereof are listed below.

In one embodiment, the calcined form of the molecular sieve in thecatalyst has a powder X-ray diffraction pattern collected inBragg-Brentano geometry with a variable divergence slit using Cu K-alpharadiation essentially as shown in the following Table:

Relative 2-Theta (°) d-spacing (Å) peak area Peak character 7.45-7.5411.85-11.72 W-M Broad to sharp 9.55-9.65 9.24-9.15 VS-W Sharp to broad11.40-11.66 7.75-7.58 W-M Broad to sharp 12.90-13.04 6.85-6.78 VS-MSharp 14.07-14.21 6.29-6.23 W Sharp to broad 14.89-15.12 5.94-5.85 WBroad to sharp 16.08-16.27 5.50-5.44 VS-W Sharp to broad 17.17-17.345.16-5.11 W-S Broad to sharp 17.71-18.00 5.00-4.92 VS-M Sharp

where the relative areas of the observed peaks in the 2-Theta range 7-19degrees are shown according to: W=weak: 0-20%; M=medium: 20-40%;S=strong: 40-60% and VS=very strong: 60-100%.

In further an embodiment, the molecular sieve belonging to the ABC-6framework family with disorder in the ABC stacking sequence belongs tothe disordered CHA-GME series.

In still an embodiment, the amount of stacking disorder of the molecularsieve is between 1 and 99%.

In an embodiment, crystals of the molecular sieve have a bipyramidal,elongated bipyramidal or capped bipyramidal morphology.

In another embodiment, the silica-to-alumina mole ratio of the molecularsieve is between 8 and 40.

In a preferred embodiment, the silica-to-alumina mole ratio is between10 and 20.

In a further embodiment, at least a part of the aluminum and/or siliconin the molecular sieve is substituted by one or more metals selectedfrom tin, zirconium, titanium, hafnium, germanium, boron, iron, indiumand gallium.

In another embodiment, the catalyst molecular sieve of the catalystcomprises copper and/or iron.

A further aspect of the invention is use of the catalyst in specificcatalytic reactions.

Specific embodiments of the use of the catalyst are the following.

One embodiment is a method for the conversion of nitrogen oxides tonitrogen in presence of a reductant comprising the step of contactingthe nitrogen oxides and the reductant with the catalyst according to anyone of the above embodiments of the catalyst.

In a preferred embodiment of the above method, the reductant compriseshydrocarbons and/or ammonia or a precursor thereof.

In a further embodiment of the above method for the conversion ofnitrogen oxides to nitrogen, the nitrogen oxides are contained in engineexhaust.

In still an embodiment of the above method for the conversion ofnitrogen oxides to nitrogen, the nitrogen oxides are contained inexhaust from a gas turbine.

In another embodiment of the above method for the conversion of nitrogenoxides to nitrogen, the nitrogen oxides comprise nitrous oxide.

In further an embodiment, the catalyst is used in a method for theselective oxidation of ammonia to nitrogen a comprising the step ofcontacting the ammonia with the catalyst.

In an embodiment, the catalyst is used in the above method for theselective oxidation of ammonia to nitrogen is combined with an oxidationfunctionality.

In still an embodiment, the catalyst is used in the above method for theselective oxidation of ammonia to nitrogen, the catalyst is locateddownstream of a selective catalytic reduction catalyst wherein an excessof ammonia is used to reduce nitrogen oxides.

Another embodiment of the use of the catalyst, is a method for thesimultaneous oxidation of hydrocarbons, carbon monoxide and reduction ofnitrogen oxides comprising the step of contacting the hydrocarbons,carbon monoxide and the nitrogen oxides with the catalyst.

In an embodiment of the method for the simultaneous oxidation ofhydrocarbons, carbon monoxide and reduction of nitrogen oxides, themolecular sieve of the catalyst comprises one or more platinum groupmetals.

Another embodiment of the use of the catalyst is a method for theconversion of oxygenates to hydrocarbons comprising the step ofcontacting the oxygenates with the catalyst.

In an embodiment of the method for the conversion of oxygenates tohydrocarbons, the hydrocarbons produced are mainly olefins.

Another embodiment of the use of the catalyst, is a method for partialoxidation of methane to methanol and/or dimethyl ether comprising thestep of contacting the methane with the catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is Simulated XRPD patterns from DIFFaX of the stacking disorderedCHA-GME series;

FIG. 2 is an XRPD of the as-prepared molecular sieve prepared in Example1 with approximate 5% disorder in the CHA-GME series (see FIG. 1);

FIG. 3 is a Scanning Electron Microscopy (SEM) image of theas-synthesized molecular sieve prepared in Example 1;

FIG. 4 is an XRPD of the calcined molecular sieve prepared in Example 1;

FIG. 5 is an XRPD of material prepared in Example 2 with approximate 20%disorder in the CHA-GME series (see FIG. 1);

FIG. 6 is a Scanning Electron Microscopy (SEM) image of theas-synthesized molecular sieve prepared in Example 2;

FIG. 7 is an XRPD of the calcined molecular sieve prepared in Example 2;

FIG. 8 is an XRPD of material prepared in Example 3 with approximate 40%disorder in the CHA-GME series (see FIG. 1);

FIG. 9 is a Scanning Electron Microscopy (SEM) image of theas-synthesized molecular sieve prepared in Example 3;

FIG. 10 is an XRPD of the calcined molecular sieve prepared in Example3;

FIG. 11 is an XRPD of material prepared in Example 4 with approximate70% faulting probability in the CHA-GME series (see FIG. 1);

FIG. 12 is a Scanning Electron Microscopy (SEM) image of theas-synthesized molecular sieve prepared in Example 4;

FIG. 13 is an XRPD of the calcined molecular sieve prepared in Example4;

FIG. 14 shows measured NOx conversion in presence of fresh (non-aged)copper loaded molecular sieve prepared according to Example 2 and inpresence of reference Cu-CHA;

FIG. 15 shows measured NOx conversion in presence of aged (700° C. for16 h in the presence of H2O) copper loaded molecular sieve preparedaccording to Example 2 and in presence of reference Cu-CHA.

The term framework type or framework topology as used herein, refers tothe unique atomic structure of a specific molecular sieve, named by athree letter code devised by the International Zeolite Association[Atlas of Zeolite Framework Types, 6th revised edition, 2007, Ch.Baerlocher, L. B. McCusker and D. H. Olson, ISBN: 978-0-444-53064-6].When stacking disorder occurs, the material cannot be described by asingle well-defined unit cell and it is therefore non-periodic in one ormore dimensions. Herein, this type of material is referred as disorderedmaterials or as materials with disorder in the stacking sequence.Materials of this type are well-known to a person skilled in the art andare often also referred to as intergrowth structures. Specifically,materials belonging to the stacking disordered CHA-GME series are oftenalso be described as intergrowths of the two end-member frameworktopologies.

In the preparation of the novel molecular sieve comprised of thecatalyst according to the invention, belonging to the ABC-6 frameworkfamily with disorder in the ABC stacking sequence essentially composedof double-six-ring periodic building units with high silica-to-aluminaratios, at least an organic structure directing agent (OSDA) incombination with at least some amount of a crystalline molecular sievewith 6-rings contained in the structure is used. The OSDA is a cationwith the generic structure described as [NR¹R²R³R⁴]⁺, wherein at leastthree of the R-groups are linear alkyl groups with one to four carbonatoms.

The OSDA cations are associated with anions, which can be hydroxide,chloride, bromide, iodide etc. as long as they are not detrimental tothe formation of the molecular sieve.

The novel molecular sieve is typically prepared by forming 1) a mixturecomprising at least the OSDA, a crystalline molecular sieve, a source ofalkali or earth alkali, hydroxide ions and water. Optionally anadditional source of silicon and an additional source aluminium or asource of both silicon and aluminium is used 2) exposing the mixture toconditions capable of crystallizing the molecular sieve and 3)separating the molecular sieve product.

The overall molar composition of the synthesis mixture from which themolecular sieve product can be synthesized is provided in Table 1.

TABLE 1 Component Broad range Preferred range SiO2/Al2O3  8-60 10-40OSDA/SiO2 0.01-1.0 0.05-0.60 A/SiO2 0.01-1.0 0.05-0.60 OH/SiO2 0.01-1.50.1-1.2 H2O/SiO2   2-200  5-100

Examples of crystalline molecular sieves that can be used include FAU,GME, LEV, AEI, LTA, OFF, CHA and ERI type molecular sieves.

Examples of OSDAs include the following cations: tetraethylammonium,methyltriethylammonium, propyltriethylammonium, diethyldipropylammonium,diethyldimethylammonium, choline etc.

Preferably, tetraethylammonium is used in the method according to theinvention.

Optional additional sources of aluminium include oxides and salts, suchas alumina, boehmite, aluminates, hydroxides, chlorides, nitrates,sulfates etc.

Optional additional sources of silicon include oxides, salts andalkoxides, such as silica, fumed silica, silicic acid, silicates,colloidal silica, tetraalkyl orthosilicates etc.

Optional additional sources of both silicon and aluminium includeoxides, clays and previously synthesized materials such as precipitatedsilica-alumina, amorphous silica-alumina, kaolin, ordered mesoporousmaterials etc.

Other tetravalent elements can also be introduced into the synthesismixture. Such elements include tin, zirconium, titanium, hafnium,germanium and combinations thereof.

Trivalent elements can also be included into the synthesis mixtureeither together with aluminium or without the presence of aluminium.Such trivalent elements include boron, iron, indium, gallium andcombinations thereof. Both tetravalent and trivalent elements may beadded in the form of metals, salts, oxides, sulphides and combinationsthereof.

Transition metals can be included in the synthesis mixture either assimple salts or as complexes that protects the transition metal fromprecipitation under the caustic conditions dictated by the synthesismixture. Especially, polyamine complexes are useful for protectingtransition metal ions of copper and iron during preparation and can alsoact to direct the synthesis towards specific molecular sieves (see forexample the use of polyamines in combination with copper ions in USPatent application 2016271596). In such a way transition metal ions canbe introduced into the interior of the molecular sieve already duringcrystallization.

The synthesis mixture can also contain inexpensive pore-filling agentsthat can help in the preparation of more siliceous products. Such porefilling agents could be crown-ethers, simple amines and other unchargedmolecules.

The synthesis mixture can also comprise seed crystals of molecularsieves. Molecular sieve crystals belonging to the ABC-6 family arepreferred such as CHA, GME or molecular sieves belonging to thedisordered CHA-GME series. The amount of seed crystals can vary from 0.1to 25% based on the total amount of silica in the synthesis mixture.

It was further observed that the presence of crystalline molecularsieves in the synthesis mixture makes it possible to extend thecomposition of the prepared product to higher silica-to-alumina ratioscompared to what is possible with traditional sources of silicon andaluminium. As already mentioned above, the highest silica-to-aluminaratio for a disordered CHA-GME type molecular sieve is for LZ-276, whichhas a reported silica-to-alumina ratio of 7.7-7.8 [U.S. Pat. No.5,248,491; G. W. Skeels, M. Sears, C. a. Bateman, N. K. McGuire, E. M.Flanigen, M. Kumar, R. M. Kirchner, Microporous Mesoporous Mater. 1999,30, 335-346.] and a morphology described as spherical intergrowths ofdisc-shaped particles, which may not be useful in several applications,whereas the morphology of the crystals prepared by the method accordingto invention is bipyramidal, elongated bipyramidal or cappedbipyramidal.

The amount of stacking disorder is controlled by variation of the amountof OSDA, alkali and hydroxide in the synthesis mixture. By variation ofthe composition of the synthesis mixture, the amount of stackingdisorder in the obtained molecular sieve product can be varied fromabout 1% to about 99%.

Crystallization of the synthesis mixture to form the novel molecularsieve is performed at elevated temperatures until the molecular sieve isformed. Hydrothermal crystallization is usually conducted in a manner togenerate an autogenous pressure at temperatures from 100-200° C. in anautoclave and for periods of time between two hours and 20 days. Thesynthesis mixture can be subjected to stirring during thecrystallization.

Once the crystallization has completed, the resulting solid molecularsieve product is separated from the remaining liquid synthesis mixtureby conventional separation techniques such as decantation, (vacuum-)filtration or centrifugation. The recovered solid crystals are thentypically rinsed with water and dried using conventional methods (e.g.heating to 75-150° C. under atmospheric pressure, vacuum drying orfreeze-drying etc.) to obtain the ‘as-synthesized’ molecular sieve. The‘as-synthesized’ product refers to the molecular sieve aftercrystallization and prior to removal of the structure directing agent(s)or other organic additives. The typical composition of the molecularsieve, in its anhydrous state, obtained by the process according to theinvention, is summarized in Table 2.

TABLE 2 Component Broad range Preferred range SiO2/Al2O3  8-60  8-40OSDA/SiO2 0.01-0.5 0.05-0.40 A/SiO2 0.01-0.5 0.05-0.40

The molecular sieve prepared by the above described method belongs tothe ABC-6 framework family with disorder in the ABC stacking sequence,essentially composed of double-six-ring periodic building units.

Its as-synthesized form is characterized by X-ray diffraction pattern,which will vary with the amount of stacking disorder in the molecularsieve. The X-ray diffraction pattern together with the possiblevariations expressed by the peak character are summarized in Table 3Table 3 and are representative for the as-synthesized product.

TABLE 3 Characteristic powder X-ray diffraction peaks for theas-synthesized molecular sieve 2-Theta (°) d-spacing (Å) Relative peak[Cu Kalpha] [Cu Kalpha] area^(a) Peak character^(b) 7.45-7.5411.85-11.72 W-M Broad to sharp 9.55-9.65 9.24-9.15 VS-W Sharp to broad11.40-11.66 7.75-7.58 W-M Broad to sharp 12.90-13.04 6.85-6.78 S-W Sharp14.07-14.21 6.29-6.23 M-W Sharp to broad 14.89-15.12 5.94-5.85 W Broadto sharp 16.08-16.27 5.50-5.44 VS-W Sharp to broad 17.17-17.34 5.16-5.11W-S Broad to sharp 17.71-18.00 5.00-4.92 VS-S Sharp ^(a)Relative areasof the observed peaks in the 2-Theta range 7-19 degrees: W = weak:0-20%; M = medium: 20-40%; S = strong: 40-60% and VS = very strong:60-100%. Collected in Bragg-Bren-tano geometry with variable divergenceslit (10 mm sample length). ^(b)The relative peak area and the peakcharacter is described as going from the CHA end-member when increasingthe amount of stacking disorder.

The organic molecules still retained in the as-synthesized molecularsieve are in most cases, unless used in the as-synthesized form, removedby thermal treatment in the presence of oxygen. The temperature of thethermal treatment should be sufficient to remove the organic moleculeseither by evaporation, decomposition, combustion or a combinationthereof. Typically, a temperature between 150 and 750° C. for a periodof time sufficient to remove the organic molecule(s) is applied. Aperson skilled in the art will readily be able to determine a minimumtemperature and time for this heat treatment. Other methods to removethe organic material(s) retained in the as-synthesized molecular sieveinclude extraction, vacuum-calcination, photolysis or ozone-treatment.

The X-ray diffraction pattern together with the possible variations inthe peak character from the varying amount of stacking disorder aresummarized in Table 4 and are representative for the calcined productprepared by the method according to the invention and after calcination.

TABLE 4 Characteristic powder X-ray diffraction peaks of the calcinedmolecular sieve 2-Theta (°) d-spacing (Å) Relative peak [Cu Kalpha] [CuKalpha] area^(a) Peak character^(b) 7.45-7.54 11.85-11.72 W-M Broad tosharp 9.55-9.65 9.24-9.15 VS-W Sharp to broad 11.40-11.66 7.75-7.58 W-MBroad to sharp 12.90-13.04 6.85-6.78 VS-M Sharp 14.07-14.21 6.29-6.23 WSharp to broad 14.89-15.12 5.94-5.85 W Broad to sharp 16.08-16.275.50-5.44 VS-W Sharp to broad 17.17-17.34 5.16-5.11 W-S Broad to sharp17.71-18.00 5.00-4.92 VS-M Sharp ^(a)Relative areas of the observedpeaks in the 2-theta range 7-19 degrees: W = weak: 0-20%; M = medium:20-40%; S = strong: 40-60% and VS = very strong: 60-100%. Collected inBragg-Bren-tano geometry with variable divergence slit (10 mm samplelength). ^(b)The relative peak area and the peak character is describedas going from the CHA end-member when increasing the amount of stackingdisorder.

It is typically desirable to remove the remaining alkali or earth alkaliions (e.g. Na⁺) from the molecular sieve by ion-exchange or other knownmethods. Ion-exchange with ammonium and/or hydrogen are well recognizedmethods to obtain the NH₄-form or H-form of the molecular sieve. Metalions may also be included in the ion-exchange procedure or introducedseparately. The NH₄-form of the material can be converted to the H-formby simple heat treatment in a similar manner as described above.

In certain cases, it may be desirable to alter the chemical compositionof the obtained molecular sieve, such as altering the silica-to-aluminaratio. Without being bound by any order of the post-synthetictreatments, acid leaching (inorganic and organic using complexing agentssuch as EDTA etc. can be used), steam-treatment, desilication andcombinations thereof or other methods of demetallation can be useful inthis case.

To promote specific catalytic applications as disclosed hereinbefore,specific metals can be introduced into the novel molecular sieve toobtain a metal-substituted, metal-impregnated or metal-exchangedmolecular sieve. The metals are introduced as metal ions byion-exchange, impregnation, solid-state procedures and other knowntechniques. Metals can be introduced to yield essentially atomicallydispersed metal ions or be introduced to yield small clusters ornanoparticles with either ionic or metallic character.

Alternatively, metals can simply be precipitated on the surface and inthe pores of the molecular sieve. In the case where nanoparticles arepreferred, consecutive treatment in e.g. a reductive atmosphere can beuseful. In other cases, it may also be desirable to calcine the materialafter introduction of metals or metal ions.

The molecular sieve of the catalyst according to the invention isparticularly useful in heterogeneous catalytic conversion reactions,such when the molecular sieve catalyzes the reaction of molecules in thegas phase or liquid phase.

It can also be formulated for other commercially important non-catalyticapplications such as separation of gases.

The catalyst of the invention can be formed into a variety of physicalshapes useful for specific applications. For example, the catalyst canbe used in powder form or be shaped into pellets, extrudates or mouldedforms, e.g. as full body corrugated catalyst.

In shaping the catalyst, it will typically be useful to apply additionalorganic or inorganic components. For catalytic applications it isparticularly useful to apply a combination with alumina, silica,titania, various spinel structures and other oxides or combinationsthereof. It may also be formulated with other active compounds such asactive metals or other molecular sieves etc.

The catalyst can also be employed coated onto or introduced into asubstrate that improves contact area, diffusion, fluid and flowcharacteristics of the gas stream. The substrate can be a metalsubstrate, an extruded substrate or a corrugated substrate made ofceramic paper. The substrate can be designed as a flow-through design ora wall-flow design. In the latter case the gas flows through the wallsof the substrate, and in this way, it can also contribute with anadditional filtering effect.

The catalyst is typically present on or within the substrate in amountsbetween 10 and 600 g/L, preferably 100 and 300 g/L, as calculated by theweight of the catalyst per volume of the total catalyst article.

The catalyst is coated on or introduced into the substrate using knownwash-coating or impregnation techniques. Thereby, a catalyst powder issuspended in liquid media together with binder(s) and stabilizer(s). Thewash coat can then be applied on the surfaces and walls of thesubstrate. The wash coat optionally also contains binders based on TiO₂,SiO₂, Al₂O₃, ZrO₂, CeO₂ and combinations thereof.

The catalyst can also be applied as one or more layers on a substrate incombination with other catalytic functionalities or other molecularsieve/zeolite catalysts. One specific combination is a layer with anoxidation catalyst containing for example platinum or palladium orcombinations thereof. The catalyst can be additionally applied inlimited zones along the gas-flow-direction of the substrate.

The catalyst according to the invention is in particular useful asmentioned hereinbefore, in catalytic conversion of oxides of nitrogen,typically in the presence of oxygen. In particular, the catalyst can beused in the selective catalytic reduction (SCR) of oxides of nitrogenwith a reductant such as ammonia and precursors thereof, including urea.The reductant can also be one or more hydrocarbons.

For this type of application, the molecular sieve of the catalyst willtypically be loaded with a transition metal such as copper or iron orcombinations thereof, using any of the procedures described above, in anamount sufficient to catalyse the specific reaction.

In certain aspects of the invention a certain amount of alkali or earthalkali in the molecular sieve of the catalyst can be beneficial. See forexample a description of alkali and earth alkali effects on copperpromoted CHA in [F. Gao, Y. Wang, N. M. Washton, M. Kollár, J. Szanyi,C. H. F. Peden, ACS Catal. 2015, 5, 6780-6791] and beneficial role forlow silica-to-alumina ratio conventional CHA molecular sieves withoutdisorder disclosed in US Patent application US20150078989 A1.

In other applications, it may be preferred that the molecular sieve ofthe catalyst is essentially free of alkali or earth alkali.

It has been observed that the disordered molecular sieve of the catalystaccording to an embodiment of the invention loaded with copper, provideshigher NOx conversion than a pure CHA zeolite loaded with copper in theselective catalytic reduction of nitrogen oxides using ammonia as areductant. Furthermore, a higher NOx conversion is retained after severehydrothermal aging for the disordered molecular sieve according to thepresent invention compared to pure CHA loaded with copper.

When used in a method for the removal of nitrogen oxides, the catalystcomprising the molecular sieve according to the invention canadvantageous be used in the reduction of nitrogen oxides in exhaust froma vehicular (i.e. mobile) internal combustion engine or exhaust oroff-gas from a stationary source.

In these applications, an exhaust gas cleaning system can comprise oneor more of the following components: a diesel oxidation catalyst (DOC),a diesel particulate filter (DPF), a selective catalytic reductioncatalyst (SCR) and/or an ammonia slip catalyst (ASC). Such a system alsotypically comprises means for metering a reductant as well ashydrocarbons into the exhaust gas system upstream the SCR and DOC,respectively.

Preferably, the SCR catalyst consists of or comprises the catalyst ofthe invention. The SCR catalyst may also contain other active componentssuch as other molecular sieves. When the SCR catalyst is arranged in theexhaust gas cleaning system, the catalyst is exposed to hightemperatures either by the exhaust gas from the engine or during thermalregeneration of one or more of the components in the system.

In the exhaust gas cleaning system as described above, the SCR catalyst,can be arranged between the DPF and the ASC components. Anotherpossibility is to arrange the SCR catalyst up-stream of the DOC, wheresome tolerance to unburnt hydrocarbons is required. The SCR catalyst mayalso be included in the DPF or combined with the ASC into a singlecomponent with a dual function.

As mentioned hereinbefore, the catalyst according to the invention canalso be part of an ammonia slip catalyst (ASC). The ASC catalyst is usedin combination with the catalyst, and its function is to remove excessamount of ammonia that is employed in the SCR stage to remove highamounts of nitrogen oxides from the exhaust gas.

ASC-type catalysts are bifunctional catalysts. The first function isoxidation of ammonia with oxygen, which produces NOx, and the secondfunction is NH3-SCR, in which NOx and residual amounts of ammonia reactto nitrogen.

Hence, ASC catalysts consist of a combination of a catalyst active forthe oxidation of ammonia by oxygen and a component active for NH3-SCR.

The most commonly applied catalysts for the oxidation of ammonia byoxygen are based on metals like Pt, Pd, Rh, Ir, Ru, but transition metaloxides or a combination of metal oxides, for example oxides Ce, Ti, V,Cr, Mn, Fe, Co, Nb, Mo, Ta, W can also be used for this purpose. Whensuch catalysts are combined, the catalyst according to the invention,preferably loaded with copper and/or iron, provides an improved ammoniaslip catalyst.

The ammonia slip catalysts as disclosed above can also include auxiliarymaterials, for example binders and support materials for the noble metalcomponents, such as Al2O3, TiO2, SiO2. Such combinations can havedifferent forms, such as a mixture of the ammonia oxidation catalystwith the SCR-active form of the catalyst according to the invention,reactors or catalyst items in series (See examples in U.S. Pat. No.4,188,364).

In particular, the ammonia slip catalyst can be a washcoated layer of amixture of the ammonia oxidation catalyst with the SCR-active form ofthe catalyst of the invention on a monolith, or a multi-layeredarrangement washcoated on a monolith (JP3436567, EP1992409), in whichthe different layers contain different amounts of the ammonia oxidationcomponent, or of the SCR-active form of the catalyst according to theinvention, or of any combination of the ammonia oxidation component andthe SCR-active form of the catalyst of the invention.

In another configuration, the ammonia oxidation catalyst, or theSCR-active form of the catalyst of the invention, or any combination ofthe ammonia oxidation catalyst and the SCR-active form of the catalystis present in walls of a monolith (JP3793283). This configuration canfurther be combined with different combinations of washcoated layers.

Another configuration of the ASC catalyst is monolithic catalyst articlewith an inlet end and an outlet end, in which the inlet end contains anammonia oxidation catalyst, or the SCR-active form of catalyst of theinvention, or any combination of the ammonia oxidation catalyst andSCR-active form of the catalyst of the invention that is different tothe ammonia oxidation catalyst, or SCR-active form of the molecularsieve of the invention, or any combination of the ammonia oxidationcomponent and SCR-active form of the catalyst according to the inventionat the outlet end (U.S. Pat. No. 8,524,185).

Another use of the catalyst according to the invention is application inthe reduction of nitrogen oxides in the exhaust gas from a gas turbineusing ammonia or a precursor thereof as a reductant as mentionedhereinbefore. In this application, the catalyst can be arranged directlydownstream of the gas turbine and is exposed to large temperaturefluctuations during gas turbine start-up and shut-down procedures.

In certain applications, the catalyst of the invention is used in a gasturbine system with a single cycle operational mode without any heatrecovery system down-stream of the turbine. When placed directly afterthe gas turbine the catalyst is able to withstand exhaust gastemperatures up to 650° C. with a gas composition containing water.

Further applications of the catalyst according to the invention are in agas turbine exhaust treatment system in combination with a heat recoverysystem such as a Heat Recovery System Generator (HRSG). In such aprocess layout, the catalyst is arranged between the gas turbine and theHRSG. The catalyst can be also arranged in several locations inside theHRSG.

When used in the abatement of hydrocarbons and carbon monoxide inexhaust or off-gases the catalyst according to the invention istypically combined with an oxidation catalyst. The oxidation catalyst,typically composed of precious metals, such as Pt and Pd, can e.g. beplaced either up-stream or down-stream of the catalyst according to theinvention or both inside and outside of e.g. the HRSG in gas turbinesystem. The oxidation functionality can also be combined with thecatalyst into a single catalytic unit.

The oxidation functionality can be combined directly with the molecularsieve by using the molecular sieve of the catalyst as support for theprecious metals. The precious metals can also be supported onto anothersupport material and physically mixed with the molecular sieve.

The catalyst according to the invention is capable of removing nitrousoxide. In this application, the catalyst can for example be arranged incombination with a nitric acid production loop in a primary, secondaryor a tertiary abatement setup. In such an abatement lay out, thecatalyst can be used to remove nitrous oxide as well as nitrogen oxidesas separate catalytic articles or combined into a single catalyticarticle. The nitrogen oxide may be used to facilitate the removal of thenitrous oxide. Ammonia or lower hydrocarbons, including methane, mayalso be added as a reductant to further reduce nitrogen oxides and/ornitrous oxide.

When used in the conversion of oxygenates into various hydrocarbons bymeans of the catalyst according to the invention, the feedstock ofoxygenates is typically lower alcohols and ethers containing one to fourcarbon atoms and/or combinations thereof. The oxygenates can also be orcomprise carbonyl compounds such as aldehyde, ketones and carboxylicacids. Particularly suitable oxygenate compounds are methanol, dimethylether, and mixtures thereof. Such oxygenates can be converted intohydrocarbons in presence of the catalyst. In such an application, theoxygenate feedstock is typically diluted and the temperature and spacevelocity is controlled to obtain the desired product range.

A further application of the catalyst of the invention is in theproduction of lower olefins e.g. suitable for addition to a gasolinepool. In this application, the product range can be rich in aromaticcompounds. The molecular sieve of the catalyst is thereby preferably inits acidic form and will be extruded with binder materials or shapedinto pellets together with suitable matrix and binder materials asdescribed above. Other suitable active compounds such as metals andmetal ions may also be included to change the selectivity of thecatalyst towards the desired product range.

The catalyst of the invention is, as mentioned hereinbefore isadditionally useful in the partial oxidation of methane to methanol orother oxygenated compounds such as dimethyl ether.

One example of a process for the direct conversion of methane intomethanol at temperatures below 300° C. in the gas phase is provided inWO11046621A1.

When used in the partial oxidation of methane to methanol or otheroxygenated compounds, the molecular sieve of the catalyst of theinvention is loaded with an amount of copper sufficient to carry out theconversion. Typically, the catalyst will be treated in an oxidizingatmosphere where-after methane is subsequently passed over the activatedcatalyst to directly form methanol. Subsequently, the produced methanolcan be extracted by suitable methods and the active sites regenerated byanother oxidative treatment. An increase or a continuous production ofmethanol is achieved by addition of water to the reactant stream tocontinuously extract methanol without having to alter the conditionsbetween oxidative treatments and methanol formation.

The catalyst according to the invention can further be used inisomerization, cracking and hydrocracking and other reactions forupgrading oil.

It may also be used as a hydrocarbon trap e.g. from cold-start emissionsfrom various engines.

Furthermore, it can be used for the preparation of lower amines such asmethyl amine and dimethylamine by reaction of ammonia with methanol.

EXAMPLES Example 1

Preparation of ABC-6 Aluminosilicate with Approximate 5% Disorder in theCHA-GME Series

A mixture of 18.08 g tetraethylammonium hydroxide (35 wt. % aqueoussolution), 6.88 g sodium hydroxide (25 wt. % aqueous solution), 15.45 gFAU zeolite (SiO2/Al2O3=16) and 59.58 g water was prepared.

The mixture was heated in a closed Teflon lined autoclave at 150° C. fortwo days and the solid product separated by filtration and afterwardswashed with deionized water. The X-ray diffraction pattern of the driedproduct is shown in FIG. 2 and indicates and approximate 5% disorder inthe CHA-GME series.

The product had a silica-to-alumina mole ratio of 12.0 as determined byICP elemental analysis. The SEM image (FIG. 3) shows that the crystalmorphology is predominantly hexagonal bipyramidal.

The as-synthesized product was calcined at 580° C. The powder XRDpattern (FIG. 4) indicated that the material remains stable aftercalcination to remove the remaining organic structure directing agent.

Example 2

Preparation of ABC-6 Aluminosilicate with Approximate 20% Disorder inthe CHA-GME Series

A mixture of 26.08 g tetraethylammonium hydroxide (35 wt. % aqueoussolution), 9.92 g sodium hydroxide (25 wt. % aqueous solution), 14.86 gFAU zeolite (SiO2/Al2O3=16) and 49.15 g water was prepared.

The mixture was heated in a closed Teflon lined autoclave at 150° C. fortwo days and the solid product separated by filtration and afterwardswashed with deionized water. The X-ray diffraction pattern of the driedproduct is shown in FIG. 5 and indicates and approximate 20% disorder inthe CHA-GME series.

The product had a silica-to-alumina mole ratio of 9.1 as determined byICP elemental analysis. The SEM image (FIG. 6) shows that the crystalmorphology is predominantly hexagonal bipyramidal and cappedbipyramidal.

The as-synthesized product was calcined at 580° C. The powder XRDpattern (FIG. 7) indicated that the material remains stable aftercalcination to remove the remaining organic structure directing agent.

Example 3

Preparation of ABC-6 Aluminosilicate with Approximate 40% Disorder inthe CHA-GME Series

A mixture of 33.74 g tetraethylammonium hydroxide (35 wt. % aqueoussolution), 9.62 g sodium hydroxide (25 wt. % aqueous solution), 14.42 gFAU zeolite (SiO2/Al2O3=16) and 42.22 g water was prepared. The mixturewas heated in a closed Teflon lined autoclave at 150° C. for two daysand the solid product separated by filtration and afterwards washed withdeionized water.

The X-ray diffraction pattern of the dried product is shown in FIG. 8indicates an approximate 40% disorder in the CHA-GME series.

The product had a silica-to-alumina mole ratio of 8.3 as determined byICP elemental analysis. The SEM image (FIG. 9) shows that the crystalmorphology is predominantly hexagonal capped bipyramidal.

The as-synthesized product was calcined at 580° C. The powder XRDpattern (FIG. 10) indicates that the material remains stable aftercalcination to remove the remaining organic structure directing agent.

Example 4

Preparation of ABC-6 Aluminosilicate with Approximate 70% Disorder inthe CHA-GME Series

A mixture of 33.47 g tetraethylammonium hydroxide (35 wt. % aqueoussolution), 12.72 g sodium hydroxide (25 wt. % aqueous solution), 14.30 gFAU zeolite (SiO2/Al2O3=16) and 39.50 g water was prepared.

The mixture was heated in a closed Teflon lined autoclave at 150° C. fortwo days and the solid product separated by filtration and afterwardswashed with deionized water. The X-ray diffraction pattern of the driedproduct is shown in FIG. 11 and indicates and approximate 70% disorderin the CHA-GME series.

The product had a silica-to-alumina mole ratio of 6.5 as determined byICP elemental analysis. The SEM image (FIG. 12) shows that the crystalmorphology is predominantly elongated hexagonal capped bipyramidal

The as-synthesized product was calcined at 580° C. The powder XRDpattern (FIG. 13) indicated that the material remains substantial stableafter calcination to remove the remaining organic structure directingagent.

Examples 5-12

Use of Different FAU-Sources and Other Si- and Al-Sources

This set of examples show that various crystalline molecular sieves canbe used in the preparation of the disordered CHA-GME molecular sievewith high silica-to-alumina ratios. Furthermore, the examples illustratehow other sources of silica and alumina can also be used in combinationwith a crystalline molecular sieve.

The general procedure described in Example 1 was repeated using:different FAU zeolites in the synthesis mixture with differentsilica-to-alumina ratios (SAR), using a combination of a FAU zeolitesand an other sources of silica- and alumina as summarized in Table 5,together with the obtained product phases, silica-to-alumina ratios andamount of stacking disorder

Composition and product characteristics from Example 1-4 are alsoincluded.

TABLE 5 Initial gel composition Product characteristics Ex. SiO2/ OSDA/A/ H2O/ Cryst. SiO2/ Stacking — Al2O3 SiO2 SiO2 SiO2 Al andSi-source^(a) — Phase Al2O3 disorder (%) 1 16 0.20 0.20 20 FAU (SAR =16) 150° C., 2 days CHA-GME 12.0 5 2 16 0.30 0.30 20 FAU (SAR = 16) 150°C., 2 days CHA-GME 9.1 20 3 16 0.40 0.30 20 FAU (SAR = 16) 150° C., 2days CHA-GME 8.3 40 4 16 0.30 0.40 20 FAU (SAR = 16) 150° C., 2 daysCHA-GME 6.5 70 5 30 0.50 0.20 25 FAU (SAR = 30) 140° C., 7 days CHA-GME18.5 5 6 30 0.37 0.40 20 FAU (SAR = 30) 150° C., 2 days CHA-GME 10.4 107 20 0.40 0.40 20 FAU (SAR = 20) 150° C., 2 days CHA-GME 10.1 20 8 210.20 0.30 20 FAU (SAR = 30) 150° C., 2 days CHA-GME 10.2 5 and ASA (SAR= 10) 9 21 0.30 0.40 20 FAU (SAR = 30) 150° C., 2 days CHA-GME 10.2 50and ASA (SAR = 10) 10 16 0.20 0.30 20 FAU (SAR = 5.2) + AS 150° C., 2days CHA-GME + — — traces of GIS 11 16 0.40 0.30 20 10% CHA (SAR = 14) +150° C., 2 days CHA-GME — 40 ASA (SAR = 16) 12 28 0.40 0.30 20 FAU (SAR= 30) + 150° C., 2 days CHA-GME — 2 CHA (SAR = 14) ^(a)FAU =FAU-zeolite, ASA = amorphous silicaalumina, AS = amorphous silica

Example 13

NOx Conversion and Hydrothermal Stability

The calcined product of example 2 was ion-exchanged four consecutivetimes with NH4Cl to remove the sodium cations. Afterwards the disorderedmolecular sieve in its NH4-form was ion-exchanged with an aqueoussolution of copper(II)acetate and calcined at 500° C.

To determine NOx conversion, 5 mg of the copper-containing molecularsieve was heated in a U-shaped microreactor for 1 h at 550° C., andexposed to a total flow of 225 NmL/min of a gas containing 500 ppm NO,533 ppm NH3, 5% H2O, and 10% O2 in N2.

The catalyst was then stepwise cooled to 160° C. using the same flow andgas composition. In each step the NOx conversion was determined bymeasuring the outlet concentrations.

For comparison a reference Cu-CHA (SiO2/Al2O3=14) was also tested.

FIG. 14 shows measured NOx conversion over fresh (non-aged) copperloaded molecular sieve prepared according to Example 2 and the referenceCu-CHA catalyst.

After the measurement of NOx conversion, the temperature was raised to700° C. for 16 h in a gas containing 10% H2O and 10% O2, where-after themeasurement of NOx conversion was repeated again. This is a measurementafter severe hydrothermal aging.

FIG. 15 shows the measured NOx conversion over aged copper loadedmolecular sieve after the described hydrothermal aging.

As evident from FIG. 14 and FIG. 15, the disordered molecular sieveaccording to the invention shows improved NOx conversion performanceboth in the fresh state and after severe hydrothermal aging despite thelower silica-to-alumina ratio of the copper-loaded disordered molecularsieve compared to the reference Cu-CHA.

1. Catalyst comprising a molecular sieve belonging to the ABC-6framework family with disorder in the ABC stacking sequence essentiallycomposed of double-six-ring periodic building units and having a moleratio of silicon oxide to aluminum oxide from about 8 to about
 60. 2.The catalyst according to claim 1, wherein the calcined form of themolecular sieve has a powder X-ray diffraction pattern collected inBragg-Brentano geometry with a variable divergence slit using Cu K-alpharadiation essentially as shown in the following Table: Relative 2-Theta(°) d-spacing (Å) peak area Peak character 7.45-7.54 11.85-11.72 W-MBroad to sharp 9.55-9.65 9.24-9.15 VS-W Sharp to broad 11.40-11.667.75-7.58 W-M Broad to sharp 12.90-13.04 6.85-6.78 VS-M Sharp14.07-14.21 6.29-6.23 W Sharp to broad 14.89-15.12 5.94-5.85 W Broad tosharp 16.08-16.27 5.50-5.44 VS-W Sharp to broad 17.17-17.34 5.16-5.11W-S Broad to sharp 17.71-18.00 5.00-4.92 VS-M Sharp

where the relative areas of the observed peaks in the 2-Theta range 7-19degrees are shown according to: W=weak: 0-20%; M=medium: 20-40%;S=strong: 40-60% and VS=very strong: 60-100%.
 3. The catalyst of claim1, wherein the molecular sieve belongs to the disordered CHA-GME series.4. The catalyst according to claim 1, wherein the amount of stackingdisorder of the molecular sieve is between 1 and 99%.
 5. The catalystaccording to claim 1, wherein crystals of the molecular sieve have abipyramidal, elongated bipyramidal or capped bipyramidal morphology. 6.The catalyst according to claim 1, wherein the silica-to-alumina moleratio of the molecular sieve is between 8 and
 40. 7. The catalystaccording to claim 1, wherein the silica-to-alumina mole ratio of themolecular sieve is between 10 and
 20. 8. The catalyst according to claim1, wherein at least a part of the aluminum and/or silicon of themolecular sieve is substituted by one or more metals selected from tin,zirconium, titanium, hafnium, germanium, boron, iron, indium andgallium.
 9. The catalyst according to claim 1, wherein the catalystand/or the molecular sieve further comprises copper and/or iron.
 10. Amethod for the conversion of nitrogen oxides to nitrogen in presence ofa reductant comprising the step of contacting the nitrogen oxides andthe reductant with the catalyst according to claim
 1. 11. The method ofclaim 10, wherein the reductant comprises hydrocarbons and/or ammonia ora precursor thereof.
 12. The method of claim 10, wherein the nitrogenoxides are contained in engine exhaust.
 13. The method of claim 10,wherein the nitrogen oxides are contained in exhaust from a gas turbine.14. The method of claim 10, wherein the nitrogen oxides comprise nitrousoxide.
 15. A method for the selective oxidation of ammonia to nitrogencomprising the step of contacting the ammonia or a gas comprising theammonia with the catalyst according to claim
 1. 16. The method of claim15, wherein the catalyst is combined with an oxidation functionality orcatalyst.
 17. The method of claim 15, wherein the catalyst is arrangeddownstream of a selective catalytic reduction catalyst and wherein anexcess of ammonia is used to reduce nitrogen oxides.
 18. A method forthe simultaneous oxidation of hydrocarbons and carbon monoxide and thereduction of nitrogen oxides comprising the step of contacting thehydrocarbons, carbon monoxide and the nitrogen oxides with a catalystaccording to claim
 1. 19. The method of claim 18, wherein the catalystfurther comprises one or more platinum group metals.
 20. A method forthe conversion of oxygenates to hydrocarbons comprising the step ofcontacting the oxygenates with a catalyst according to claim
 1. 21. Themethod according to claim 20, wherein the hydrocarbons produced areprimarily olefins.
 22. A method for partial oxidation of methane tomethanol and/or dimethyl ether comprising the step of contacting themethane with a catalyst according to claim 1.